Benzyl esters of n-perfluoro methyl carbamate

ABSTRACT

THIS INVENTION DISCLOSES NEW CHEMICAL COMPOUNDS OF THE FORMULA   (F3C-NH-COO-(CH2)N-),(X)M,(H)(5-M)-BENZENE   WHEREIN X IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKOXY, HALOGEN AND DIALKYLAMINO; M IS AN INTEGER FROM 0 TO 5; AND N IS AN INTEGER FROM 1 TO 3. THIS INVENTION FURTHER DISCLOSES NEW PESTICIDAL COMPOSITIONS WHICH COMPRISES AN INERT CARRIER AND A PESTICIDALAMOUNT OF A COMPOUND OF THE ABOVE DESCRIPTION.

United States Patent 3,639,454 BENZYL ESTERS 0F N-PERFLUORO METHYLCARBAMATE Sidney B. Richter, Chicago, 11]., assignor to VelsrcolChemical Corporation, Chicago, Ill. No Drawing. Filed July 17, 1968,Ser. No. 745,404 Int. Cl. C07c 125/06 US. Cl. 260-482 C 6 ClaimsABSTRACT OF THE DISCLOSURE This invention discloses new chemicalcompounds of the formula wherein X is selected from the group consistingof alkyl, alkoxy, halogen and dialkylamino; m is an integer from 0 toand n is an integer from 1 to 3. This invention further discloses newpesticidal compositions which comprise an inert carrier and a pesticidalamount of a compound of the above description.

This invention relates to new chemical compositions of matter, and moreparticularly to new compounds of the formula o (CH ),,O- I IOFs XmH(5-m) wherein X is selected from the group consisting of alkyl, alkoxyhalogen and dialkylamino; m is an integer from 0 to 5; and n is aninteger from 1 to 3.

In a preferred embodiment of this invention the substituent X isselected from the group consisting of lower alkyl, lower alkoxy,chlorine, bromine and di(loweralkyl) amino; m is an integer from 0 to 3;and 'n is an integer from 1 to 3.

The compounds of the present invention are useful as pesticides,particularly as insecticides and herbicides.

The compounds of the present invention can be prepared readily byreacting an alcohol of the formula Xm Hus-m) wherein X, m and n are asheretofore described, with an equimolar amount of trifluoromethylisocyanate. This reaction can be carried out by charging the alcohol, ora solution of the alcohol in a suitable inert organic solvent, into areaction vessel and then adding the trifluoromethyl isocyanate thereto.This reaction can be performed at atmospheric pressure by bubbling thetrifluoromethyl isocyanate into the reaction medium with vigorousstirring at room temperature, or at superatomspheric pressures in asealed reaction vessel.

A convenient manner in which to effect this reaction is in a closedsystem by either adding the trifluoromethyl isocyanate under pressure,or, by first cooling the alcohol to a temperature below about -40 C.adding the isocyanate, and then sealing the reaction vessel. In someinstances this reaction can be sufficiently exothermic to requireintermittent cooling during the reaction. After the reaction iscompleted the desired product can be recovered directly, or, if asolvent was used, by stripping of the solvent under reduced pressure.The product can then be used as such as can be further purified bydistillation, if the product is a liquid, or by triturating,recrystallizing or Patented Feb. 1, 1972 benzyl alcohol,

Z-methylbenzyl alcohol, 3-methylbenzyl alcohol, 4-methylbenzyl alcohol,2-chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol,3-bromobenzyl alcohol, 4-ethylbenzyl alcohol, 4-isopropylbenzyl alcohol,4-sec-butylbenzyl alcohol, 4-chloro-3,5-dimethylbenzyl alcohol,3-bromo-2-methylbenzyl alcohol, 2,4-dichlorobenzyl alcohol,2,6-dimethylbenzyl alcohol, 3-methoxybenzyl alcohol, 3-ethoxybenzylalcohol, 5-bromo-2-methoxybenzyl alcohol, 3-sec-butoxybenzyl alcohol,2-chloro-5-methoxybenzyl alcohol, 2-butoxy-3-methoxybenzyl alcohol,2-ethoXy-4,6-dimethylbenzyl alcohol, Z-dimethylaminobenzyl alcohol,4-dimethylaminobenzyl alcohol, phenethyl alcohol, 3-methylphenethylalcohol, 4-chlorophenethyl alcohol, 3,4-dichlorophenethyl alcohol,4-bromophenethyl alcohol, 3,4-dimethylphenethyl alcohol,Z-methoxyphenethyl alcohol, 2-chloro-4,S-dimethoxyphenethyl alcohol,2-butoxyphenethyl alcohol, 3,5-dimethoxyphenethyl alcohol,2-isopropyl-3-methoxyphenethyl alcohol, 2,4,6-triethylphenethyl alcohol,4-dimethylaminophenethyl alcohol, 3-phenylpropanol,3-(4'-methylphenyl)-propanol,

3 (4'-cholrophenyl) -propanol, 3-(2'-methoxyphenyl)-propanol and thelike.

The following examples illustrate in detail the manner in which thecompounds of the present invention can be prepared.

EXAMPLE 1 Preparation of N-trifluoromethylbenzylcarbamate A solution ofbenzyl alcohol 10.8 grams; 0.1 mol) in toluene (50 ml.) is placed into asuitable pressure vessel equipped with stirring means. The solution iscooled to about -40 C. and trifluoromethyl isocyanate (11.1 grams; 0.1mol) is added thereto. The reaction vessel is then sealed and heated toa temperature of about 40 C. for a period of about 4 hours. After thistime the reaction mixture is stripped of toluene to yield the desiredproduct N-trifluoromethylbenzylcarbamate.

EXAMPLE 2 Preparation of N-trifiuoromethyl-4-chlorobenzylcarbamate Asolution of 4-chlorobenzyl alcohol (14.2 grams; 0.1 mol) in toluene (60ml.) is placed into a pressure vessel. The solution is cooled to about50 C. and trifluoromethyl isocyanate is'added thereto. The pressurevessel is then sealed and the reaction mixture is heated to 3 about 60C. for a period of about 3 hours. After this time the toluene isstripped from the reaction product to yieldN-trifluoromethyl-4-chlorobenzyl carbamate.

EXAMPLE 3 Preparation of N-trifluoromethyl-3,5- dimethylbenzylcarbamatePreparation of N-trifluoromethyl-4- dimethylaminobenzylcarbamate Asolution of 4 dimethylaminobe'nzyl alcohol (15.1 grams; 0.1 mol) intoluene (1 m1.) is placed in a glass reaction flask equipped withstirrer, reflux condenser and gas inlet tube. Trifluoromethyl isocyanate(15.0 grams; 0.13 mol) is bubbled into the solution with vigorousstirring at a temperature of about 50 C. After the addition is completedthe reaction is stirred for an additional period of about 1 hour. Afterthis time the reaction mixture is stripped of toluene to yield thedesired product N- trifluoromethyl-4-dimethylaminobenzylcarbamate.

EXAMPLE 5 Preparation of N-trifluoromethylphenethylcarbamate A solutionof phenethyl alcohol 12.2 grains; 0.1 mol) in toluene (100 ml.) isplaced into a glass reaction flask equipped with stirrer, refluxcondenser and gas inlet tube. Trifluoromethyl isocyanate (15.0 grams;0.13 mole) is bubbled into the solution with vigorous stirring at atemperature of about 50 C. After the addition is completed the reactionmixture is stirred for an additional period of about 1 hour. After thistime the reaction mixture is stripped of toluene to yield the desiredproduct N-trifluoromethylphenethylcarbamate.

EXAMPLE 6 Preparation of N-trifluoromethyl-3,4-dichlorophenethylcarbamate A solution of 3,4 dichlorophenethyl alcohol(19.1 grams; 0.1 mol) in toluene (50 ml.) is placed into a pressurevessel and is cooled in an acetone-Dry Ice bath. Trifluoromethylisocyanate (11.1 grams; 0.1 mol) is added to the cooled solution and thepressure vessel is sealed. The reaction mixture is then heated to about60 C. for a period of about 3 hours. After this time the reactionmixture is stripped of toluene under reduced pressure to yield thedesired product N-trifluoromethyl-3,4-dichlorophenethylcarbamate.

Other compounds within the scope of this invention can be prepared bythe procedures described in the foregoing examples. Presented in thefollowing examples are the essential ingredients required to prepare theindicated named compounds according to the procedure heretoforedescribed.

EXAMPLE 7 4 ethylbenzyl alcohol+trifluoromethyl isocyanate:N-trifluoromethyl-4-ethylbenzylcarbamate.

EXAMPLE -8 3 bromobenzyl alcohol-i-trifluoromethyl isocyanate:N-trifiuoromethyl-3-bromobenzylcarbamate.

4 EXAMPLE 9 3-methoxybenzyl alcohol+trifluoromethyl isocyanate:N-trifiuoromethyl-3-methoxybenzylcarbamate.

EXAMPLE 10 5-bromo-2-methoxybenzyl alcohol-l-trifiuoromethylisocyanate=N-trifluoromethyl 5 bromo-Z-methoxybenzyl carbamate.

EXAMPLE 11 4-ethylphenethyl alcohol-i-trifluoromethyl isocyanate:N-trifluoromethyl-4-ethylphenethylcarbamate.

EXAMPLE 12 2-chloro 4,5 dimethoxyphenethyl alcohol-i-trifluoromethylisocyanate=N-trifluoromethyl-2-chloro-4,S-dimethoxyphenethylcarbamate.

EXAMPLE l3 4-dimethylaminophenethyl alcohol+trifluoromethylisocyanate=N-trifluoromethyl 4 dimethylaminophenethylcarbamate.

EXAMPLE 14 3phenylpropanol+trifluoromethylisocyanate:N-trifiuoromethyl-3-phenylpropylcarbamate.

EXAMPLE 1s 3-(4'-chlorophenyl)-propanol+trifluoromethylisocyanate=N-trifiuoromethyl-3-(4 chlorophenyl)-propylcarbamate.

EXAMPLE 16 2,4-diiodobenzyl alcohol+trifluoromethyl isocyanate:N-trifluoromethyl-2,4-diiodobenzyl carbamate.

EXAMPLE l7 4 fluorobenzyl alcohol+trifluoromethy1 isocyanate:N-trifluoromethyl-4-fluorobenzy1carbamate.

EXAMPLE l8 2-chloro 4 isopropylbenzyl alcohol+trifluoromethylisocyanate:Ntrifluoromethyl 2 chloro-4-isopropy1carbamate.

EXAMPLE 19 4 pentylbenzyl alcohol+trifluoromethyl isocyanate=N-trifluoromethyl-4-pentylbenzylcarbamate.

EXAMPLE 20 3-di-n-propylaminobenzyl alcohol+trifluoromethy1isocyanate=N-trifluoromethyl -3- di n propylaminobenzylcarbamate.

EXAMPLE 21 4 dipentylaminobenzyl alcohol+trifluoromethylisocyanate=N-trifiuoromethyl 4 dipentylaminobenzylcarbamate.

EXAMPLE 22 2,6 dimethoxybenzyl alcohol+trifiuoromethylisocyanate=Ntrifluoromethyl 2,6 dimethoxybenzylcarbamate. a a

EXAMPLE 23 3 isopropoxybenzyl alcohol+trifiuoromethyl isocyanate=Ntrifluoromethyl 3 isopropoxybenzylcarbamate. 1

- EXAMPLE 24 4 hexyloxybenzyl alcohol+trifluoromethylisocyanate=N-trifluoromethyl-4-hexyloxybenzylcarbamate.

EXAMPLE 25 3,4,5 trichlorobenzyl alcohol-l-trifluorornethyl isocyanate=Ntrifluoromethyl 3,4,5 trichlorobenzylcarbamate.

EXAMPLE 26 2 dimethylamino 4,5 dibromobenzyl alcohol-l-trifluoromethylisocyanate:N-trifluoromethyl 2 dimethylamino-4,5-dibromobenzylcarbamate.

EXAMPLE 27 2 ethoxyphenethyl alcohol+trifluoromethylisocyanate=N-trifluoromethyl-2-ethoxyphenylcarbamate.

EXAMPLE 28 3-(2'-methoxy 4' bromophenyl)-propanol-|-trifluoromethylisocyanate=N trifluoromethyl-3-(2-methoxy-4'-bromophenyl)-propylcarbamate.

For practical use as pesticides, the compounds of this invention aregenerally incorporated into pesticidal compositions which comprise aninert carrier and a pesticidally toxic amount of such a compound. Suchpesticidal compositions, which can also be called formulations, enablethe active compound to be applied conveniently to the site of the pestinfestation in any desired quantity. These compositions can be solidssuch as dusts, granules, or Wettable powders; or they can be liquidssuch as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the tales, clays, silicas,pyrophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5mm. Wettable powders, which can be dispersed in water and/or oil to anydesired concentration of the active compound, can be prepared byincorporating Wetting agents into concentrated dust compositions.

In some cases the active compounds are sufliciently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofpesticides can be dispersed under superatmospheric pressure as aerosols.However, preferred liquid pesticidal compositions are emulsifiableconcentrates, which comprise an active compound according to thisinvention and as the inert carrier, a solvent and an emulsifier. Suchemulsifiable concentrates can be extended with water and/ or oil to anydesired concentration of active compound for application as sprays tothe site of the pest infestation. The emulsifiers most commonly used inthese concentrates are nonionic or mixtures of nonionic with anionicsurface-active agents.

A typical pesticidal composition according to this invention isillustrated by the following example, in which the quantities are inparts by Weight.

EXAMPLE 29 Preparation of a dust Product of Example 1 a- Powdered talc90 The above ingredients are mixed in a mechanical grinder-blender andare ground until a homogenous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the pest infestation.

When used as insecticides, the compounds of this invention can beapplied in any manner recognized by the art. One method for destroyinginsects comprises applying to the locus of the insect infestation, aninsecticidal composition comprising an inert carrier and as theessential active ingredient, in a quantity which is toxic to saidinsects, a compound of the present invention. The concentration of thenew compounds of this invention in the insecticidal compositions willvary greatly with the type of formulation and the purpose for which itis designed, but generally the insecticidal compositions will comprisefrom about 0.05 to about 95 percent by weight of the active compounds ofthis invention. In a preferred embodiment of this invention, theinsecticidal compositions will comprise from about 5 to percent byWeight of the active compound. The compositions can also comprise suchadditional substances as other pesticides, stabilizers, spreaders,deactivators, adhesives, stickers, fertilizers, activators, synergists,and the like.

The compounds of the present invention are also useful when combinedwith other insecticides in the insecticidal compositions heretoforedescribed. These other insecticides can comprise from about 5% to aboutof the active ingredients in the insecticidal compositions. Use of thecombinations of these other insecticides with the compounds of thepresent invention provide insecticidal compositions which are moreeffective in controlling insects and often provide results unattainablewith separate compositions of the individual insecticides. The otherinsecticides with Which the compounds of this invention can be used inthe insecticidal compositions to control insects, can includehalogenated compounds such as DDT, methoxychlor, TDE, lindane,chlordane, isobenzan, aldrin, dieldrin, heptachlor, endrin, mireX,endosulfon, dicofol, and the like; organic phosphorus compounds such asTEPP, schradan, ethion, parathion, methyl parathion, rEPN, demeton,'carbonphenothion, phorate, zinophos, diazinon, malathion, mevinphos,dimethoate, DBD, ronnel, oxydemeton-methyl, dicapthon, chlorothion,phosphamidon, naled, fenthion, trichlorofon, DDVP, and the like; organicnitrogen compounds such as dinitro-o-cresol, dinitrocyclohexylphenol,DNB, DNP, binapacril, azobenzene, and the like; organic carbamatecompounds such as carbaryl, ortho 5353, and the like; organic sulfurcompounds such as phenothiazine, phenoxathin, lauryl thiocyanate.[bis(2-thiocyanoethyl) ether] isobornyl thiocyanoacetate, and the like;as well as such substances usually referred to as fumigants, as hydrogencyanide, carbon tetrachloride, calcium cyanide, carbon disulfide,ethylene dichloride, propylene dichloride, ethylene dibromide, ethyleneoxide, methyl bromide, paradichlorobenzene, and the like.

The compounds of the present invention can also be combined withfungicidal and nematocidal chemical compounds to form pesticidalcompositions useful for the control of fungi and in some cases soilnematodes as well as insects. Typical examples of such fungicidalchemical compounds are ferbam, nabam, zineb, ziram, thiram, chloranil,dichlone, glyodin, cyclohexamide, dinocap, maneb, captan, dodi ne, PCNB,p-dimethylaminobenzenediazo sodium sulfonate and the like; whileexamples of nematodicidal compounds are chloropicrin, 0,0-diethylO-(2,4-dichlorophenyl) phosphorothioate, tetrachlorothiophene, dazomet,dibromochloropropane, and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects. Insecticides which are to be used as stomach poisonsor protective materials can be applied to the surface on which theinsects feed or travel. Insecticides which are to be used as contactpoisons or eradicants can be applied directly to the body of the insect,as a residual treatment to the surface on which the insect may walk orcrawl, or as a fumigant treatment of the air which the insect breathes.In some cases, the compounds applied to the soil or plant surfaces aretaken up by the plant, and the insects are poisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.Among the insects which can be effectively controlled by the compoundsof the present invention are the chewing insects such as the Mexican\bean beetle, the southern ar-myworm; the piercing-sucking insects, suchas the pea aphid, the cereal leaf beetle, the house fly, the grapeleafhopper, the chinch bug, the lygus bugs, oyster shell scale, theCalifornia red scale, the Florida red scale, the

soft scale and mosquitoes; the internal feeders, including borers suchas the European corn borer, the peach twig borer and the corn earworm,worms or weevils such as the codling moth, alfalfa weevil, cotton bollweevil, pink boll worm, plum curoulio, red banded leaf roller,melonworm, cabbage looper and apple maggot, leaf miners such as theapple leaf miner, birch leaf miner and beet leaf miner, and gall insectssuch as the wheat joint worm and the grap phylloxera. Insects whichattack below the surface of the ground are classified as subterraneaninsects and include such destructive pests as the wooly apple aphid, theJapanese beetle, the onion maggot and the corn rootworm.

Mites and ticks are not true insects. Many economically importantspecies of mites and ticks can be controlled by the compounds of thispresent invention such as the red spider mite, the two spotted mite, thestrawberry spider mite, the citrus rust mite, the cattle tick, thepoultry mite, the citrus red mite and the European red mite. Chemicalsuseful for the control of mites are often called miticides, while thoseuseful for the control of both mites and ticks are known specifically asacaricides.

The quantity of active compound of this invention to be used for insectcontrol will depend on a variety of factors, such as the specific insectinvolved, intensity of the infestation, weather, type of environment,type of formulation, and the like. For example, the application of onlyone or two ounces of active chemical per acre may be adequate forcontrol of a light infestation of an insect under conditions unfavorablefor its feeding, while a pound or more of active compound per acre maybe required for the control of a heavy infestation of insects underconditions favor-able to their development.

The insecticidal utility of the compounds of the present invention canbe demonstrated in a variety of experiments well known in the art. Forexample, the effectiveness of the compounds of this invention for thecontrol of the common house fly (Musca domestica) can be shown in anexperiment wherein the test compounds are formulated as aqueousemulsions of acetone solution and are then sprayed on fifty adult flieswhich have been placed into screen cages. The mortality of the flies isthen determined after a period of 48 hours and rated in comparison withuntreated controls. The results of this experiment demonstrate theutility of the compounds of this invention as insecticides.

When used as herbicides the compounds of this invention can be appliedin any manner recognized by the art. One method for the control of weedscomprises contacting the locus of said weeds with a herbicidalcomposition comprising an inert carrier and as an essential activeingredient, in a quantity which is herbicidally toxic to said weeds, acompound of the present invention. The concentration of the newcompounds of this invention in the herbicidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the herbicidal compositions will comprise fromabout 0.05 to about 95 percent by weight of the active compounds of thisinvention. In a preferred embodiment of this invention, the herbicidalcompositions will comprise from about 5 to about 75 percent by weight ofthe active compound. The compositions can also comprise such additionalsubstances as other pesticides, such as insecticides, nematocides,fungicides, and the like; stabilizers; spreaders; deactivators;adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, dessicants, growth inhibitors,and the like in the herbicidal compositions heretofore described. Theseother materials can comprise from about 5% to about 95% of the activeingredients in the herbicidal compositions, Use of combinations of theseother herbicides and/or defoliants, dessicants, etc. with the compoundsof the present invention provide herbipidal compositions which are moreeffective in controlling weeds and often provide results unattainablewith separate compositions of the individual herbicides. The otherherbicides, defoliants, dessicants and plant growth inhibitors, withwhich the compounds of this in vention can be used in the herbicidalcompositions to control weeds, can include chlorophenoxy herbicides suchas 2,4-D, 2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP,2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicidessuch as IPC, CIPC, swep, barban, BCBC, CEPC, CPPC, and the like;thiocarbamate and dithiocarbamate herbicides such as CDEC, methamsodium, EPTC, diallate, PEBC, perbulate, vernolate and the like;substituted urea herbicides such as norea, siduron, dichloral urea,chloroxuron, cycluron, fenuron, monuron, monuron TCA diuron, linuron,monolinuron, neburon, buturon, trimetom and the like; symmetricaltriazine herbicides such as simazine, chlorazine atratone, desmetryne,norazine, ipazine, prometryn, atrazine, trietazine, simetone, prometone,propazine, ametryne, and the like; chloroacetamide herbicides such asalpha-chloro N,N dimethylacetamide, CDEA, CDAA,al'pha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,4-(chloroacetyl)morpholine, l-(chloroacetyl) piperidine, and the like;chlorinated aliphatic acid herbicides such as TCA, dalapon,2,3-dichloropropionic acid, 2,2,3-TPA and the like, chlorinated benzoicacid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6- TBA,dicamba, tricamba, amiben, fenac, PBA,Z-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-m'trobenzoicacid and the like;

and such compounds as aminotriazole, maleic hydrazide,

phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl2,3,5,6 tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil;DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA,O-S-dimethyl tetrachlorothioterephthalate, methyl 2,3,5,6 tetrachloro Nmethoy-N-methyl terephthalamate, 2. [(4 chloro-o-tolyl)-oxy]-N-methoxyacetamide, DSMA, MSMA, potassium azide, acrolein, benefin,bensulide, AMS, bromacil, bromoxynil, cacodylic acid, CMA, CPMF,cypromid, DDB, DCPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA,ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH,molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor,sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H-732,M-2901, planavin, sodium tetraborate, calcium cyanarnid, DEF, ethylxanthogen disulfide, sindone, sindone B, propanil and the like.

Such herbicides can also be used in the methods and compositions of thisinvention in the form of their salts, esters, amides, and otherderivatives whenever applicable to the particular parent compounds.

Weeds are undesirable plants growing where they are not wanted, havingno economic value, and interfering with the production of cultivatedcrops, with the growing of ornamental plants, or with the welfare oflivestock. Many types of weeds are known, including annuals such aspigweed, lambsquarters, foxtail, crabgrass, wild mustard, fieldpennycress, ryegrass, goose-grass, chickweed, wild oats, velvet leaf,purselane, barnyard grass, smartweed, knotweed, cocklebur, wildbuckheat, kochia, medic corn cockle, ragweed, sowthistle, coifee-weed,croton, cuphea, dodder, fumitory, groundsel, hemp nettle, knowel,spurge, spurry, emex, jungle rice, pondweed, dog fennel, carpetweed,morning glory, bedstraw, ducksalad and naiad; biennials such as wildcarrot, matricaria, wild barley, campion, chamomile, burdock, mullein,roundleaved mallow, bull thistle, hounds-tongue, moth mullein, andpurple star thistle; or perennials such as while cockle, perennialrye-grass, quackgrass, Johnson grass, Canada thistle, hedge bindweed,Bermuda grass, sheet sorrel, curly dock, nutgrass, field chickweed,dandelion, campanula, field bindweed, Russian knapweed, mesquite,toadflax,

yarrow, aster, gromwell, horsetail, ironweed, sesbania, bulrush, cattailand winter-cress.

Similarly, such weeds can be classified as broadleaf or grassy weeds. Itis economically desirable to control the growth of such weeds withoutdamaging beneficial plants or livestock.

The new compounds of this invention are particularly valuable for weedcontrol because they are toxic to many species and groups of weeds whilethey are relatively non-toxic to many beneficial plants. The exactamount of compound required will depend on a variety of factors,including the hardiness of the particular weed species, weather, type ofsoil method of application, the kind of beneficial plants in the samearea, and the like. Thus, while the application of up to only about oneor two ounces of active compound per acre may be sufiicient for goodcontrol of a light infestation of weeds growing under adverseconditions, the application of ten pounds or more of active compound peracre may be required for good control of a dense infestation of hardyperennial weeds growing under favorable conditions.

The herbicidal toxicity of the new compounds of this invention can beillustrated by many of the established testing techniques known to theart, such as preand post-emergence testing.

The herbicidal activity of the compounds of this invention can bedemonstrated by experiments carried out for the pre-emergence control ofa variety of weeds. In these experiments small plastic greenhouse potsfilled with dry soil are seeded with the weed seeds. Twenty-four hoursor less after seeding the pots are sprayed with water until the soil iswet and the test compounds, formulated as aqueous emulsions of acetonesolutions containing emulsifiers, are sprayed on the surface of thesoil.

After spraying, the soil containers are placed in the greenhouse andprovided with supplementary heat as required and daily or more frequentwatering. The plants are maintained under these conditions for a periodof from 15 to 21 days, at which time the condition of the plants and thedegree of injury to the plants is rated on a scale of from to 10, asfollows: 0=no injury, 1,2=slight injury 3.4=moderate injury,5,6=moderately severe injury, 7,8,9=severe injury and =death. Theresults of these experiments demonstrate the effectiveness of thecompounds as herbicides.

The herbicidal activity of the compounds of this invention can also bedemonstrated by experiments carried out for the post emergence controlof various weeds. In these experiments the compounds to be tested areformulated as aqueous emulsions and sprayed on the foliage of the Weedsthat have attained a prescribed size. After spraying the plants areplaced in a greenhouse and watered daily or more frequently. Water isnot applied to the foliage of the treated plants. The severity of theinjury is determined 10 to 15 days after treatment and is rated on thescale of from 0 to 10 heretofore described. The effectiveness of thesecompounds as herbicides is demonstrated by the results of thisexperiment.

I claim:

1. A compound of the formula References Cited UNITED STATES PATENTS8/1968 Harrett, et al. 260482 C 5/1969 DAmico 260482 XC LEWIS GOTTS,Primary Examiner P. I. KILLOS, Assistant Examiner U.S. Cl. X.R. 71-106;424300

